Poly(ether ketone ketone) polymers, corresponding synthesis methods and polymer compositions and articles made therefrom

ABSTRACT

Described herein are poly(ether ketone ketone) (“PEKK”) polymers having improved processability. It was surprisingly discovered that by selectively controlling the relative amounts of reactants during the synthesis, PEKK polymers having unexpectedly lower melt viscosities can be obtained. More particularly, by selectively controlling the relative amounts of monomers used to form recurring units of the PEKK polymer, in conjunction with selective control of other reaction components, the resulting PEKK polymers had reduced viscosities, relative to PEKK polymers synthesized by using tradition reaction schemes (“traditional PEKK polymers”). By providing PEKK polymers with lower melt viscosities, the PEKK polymers described herein have improved processability.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 16/471,536filed on Jun. 19, 2019 (allowed), which claims priority to U.S.Provisional Application No. 62/437,300 filed Dec. 21, 2016, U.S.Provisional Application No. 62/456,941 filed Feb. 9, 2017, and EuropeanApplication No. EP 17169170.2 filed May 3, 2017, the whole content ofthese applications being incorporated herein by reference for allpurposes.

FIELD OF THE INVENTION

The invention relates to poly(ether ketone ketone) polymers. Theinvention further relates to the synthesis of poly(ether ketone ketone)polymers. The invention still further relates to polymer compositionsincluding the poly(ether ketone ketone) polymers and articles madetherefrom.

BACKGROUND OF THE INVENTION

Poly(ether ketone ketone) (“PEKK”) polymers are well suited for use inrelatively extreme conditions. In part, due to the high crystallinityand high melt temperature of PEKK polymers, they have excellent thermal,physical and mechanical properties. Such properties make PEKK polymersdesirable in a wide range of demanding application settings including,but not limited to, aerospace and oil and gas drilling. Nevertheless,the same high crystallinity and high melt temperatures that provide manyof the benefits of PEKK polymers also present difficulties inprocessing. Accordingly, there is an ongoing need to develop PEKKpolymers having improved processability.

DETAILED DESCRIPTION OF THE INVENTION

Described herein are poly(ether ketone ketone) (“PEKK”) polymers havingimproved processability. It was surprisingly discovered that byselectively controlling the relative amounts of reactants during thesynthesis, PEKK polymers having unexpectedly lower melt viscosities canbe obtained. More particularly, by selectively controlling the relativeamounts of monomers used to form recurring units of the PEKK polymer, inconjunction with selective control of other reaction components, theresulting PEKK polymers had reduced viscosities, relative to PEKKpolymers synthesized by using tradition reaction schemes (“traditionalPEKK polymers”). By providing PEKK polymers with lower melt viscosities,the PEKK polymers described herein have improved processability.

Furthermore, compared with PEKK polymers synthesized using anelectrophilic synthesis route, the PEKK polymers described herein hassignificantly lower chlorine concentrations as well as significantlyimproved thermal stability. Due to the halogenated acid used to generatethe intermediate carbocation during electrophilic substitution, PEKKpolymers synthesized using an electrophilic synthesis scheme have asignificantly elevated residual chlorine concentration, relative to PEKKpolymers synthesized via nucleophilic routes. Correspondingly, PEKKpolymers synthesized by electrophilic routes must undergo a significantamount of purification to reduce chlorine concentration, for example,for use in consumer electronic device application settings whichgenerally require a chlorine concentration of less than 900 parts permillion by weight (“ppm”). In commercially relevant processes (e.g.large scale polymer manufacturing), the costs associated with removal ofchlorine can be significant, due to the economies of scale. Accordingly,the PEKK polymers described herein using a nucleophilic synthesis routecan provide significant reduction in large scale production costs.Additionally, because PEKK polymers synthesized using an electrophilicroute have lower thermal stability, there is a significantly higher rateof defects in parts made from such PEKK polymers, relative to PEKKpolymers synthesized using a nucleophilic route as described here.

The Poly(Ether Ether Ketone) Polymers

The PEKK polymers of interest herein contain at least one recurring unit(R^(M) _(PEKK)) and at least one recurring unit (R^(P) _(PEKK)). Eachrecurring unit (R^(M) _(PEKK)) is represented by a formula according tothe general formula:

-[-M_(m)-O—]—, and  (1)

each recurring unit (R^(P) _(PEKK)) is represented by a formulaaccording to the following general formula:

-[-M_(p)-O—]—,  (2)

where M_(m) and M_(p) are represented by the following general formulae,respectively:

In Formulae (3) and (4), R¹ and R², at each instance, is independentlyselected from the group consisting of an alkyl, an alkenyl, an alkynyl,an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide,an imide, an alkali or alkaline earth metal sulfonate, an alkylsulfonate, an alkali or alkaline earth metal phosphonate, an alkylphosphonate, an amine, and a quaternary ammonium; and i and j, at eachinstance, is an independently selected integer ranging from 0 to 4. Asused herein, a dashed bond indicates a bond to an atom outside of thedrawn structure. The subscripts “p” and “m” on the species “M” reflectthe respective para (Formulae (4)) and meta (Formula (3)) benzoylsubstitutions on the central benzene ring. In some embodiments, each iand j are zero. For clarity, in some embodiments, the PEKK polymer has aplurality of recurring units (R^(M) _(PEKK)), a plurality of recurringunit (R^(P) _(PEKK)), or both, with each recurring unit being distinct.Accordingly, reference to recurring units (R^(M) _(PEKK)) references alltypes of recurring units in PEKK according to general Formula (1) andreference to recurring units (R^(P) _(PEKK)) references all types ofrecurring units in PEKK according to general Formula (2).

As used herein, a PEKK polymer refers to any polymer in which the totalconcentration of recurring units (R^(M) _(PEKK)) and recurring units(R^(P) _(PEKK)) is at least 50 mol %, relative to the total number ofmoles of recurring unit in the PEKK polymer. In some embodiments, thetotal concentration of recurring units (R^(M) _(PEKK)) and recurringunits (R^(P) _(PEKK)) is at least 60 mol %, at least 70 mol %, at least80 mol %, at least 90 mol %, at least 95 mol % or at least 99 mol %,relative to the total number of moles of recurring units in the PEKKpolymer. In some embodiments, the ratio of the total number of moles ofrecurring units (R^(P) _(PEKK)) to the total number of moles ofrecurring units (R^(M) _(PEKK)) (“(R^(P) _(PEKK))/(R^(M) _(PEKK))ratio”) is at least about 1:1, at least about 1.2:1, at least about1.3:1, at least about 1.4:1. Additionally or alternatively, the (R^(P)_(PEKK))/(R^(M) _(PEKK)) ratio is no more than about 5.7:1, no more thanabout 5:1, no more than about 4:1, no more than about 3.5:1 or no morethan about 3:1, or no more than about 2.7:1.

In some embodiments, recurring units (R^(M) _(PEKK)) include a recurringunit (R^(M) _(PEKK)) and recurring (R^(P) _(PEKK)) includes recurringunits (R^(P1) _(PEKK)), (R^(P2) _(PEKK)), and (R^(P3) _(PEKK)).Recurring units (R^(M1) _(PEKK)), (R^(P1) _(PEKK)), (R^(P2) _(PEKK)) and(R^(P3) _(PEKK)) are represented by the following formulae,respectively:

-[-M¹*_(m)-O—]—,  (5)

[-M¹*_(p)-O—]—,  (6)

[-M²*_(p)-O—]—,  (7)

-[-M³*_(p)-O—]—, and  (8)

where M¹*_(m), M¹*_(p), M²*_(p), and M³*_(p) are represented by thefollowing formulae, respectively:

where R¹*, R²*, R³* and R⁴*, at each instance, is independently selectedfrom the group consisting of an alkyl, an alkenyl, an alkynyl, an aryl,an ether, a thioether, a carboxylic acid, an ester, an amide, an imide,an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, analkali or alkaline earth metal phosphonate, an alkyl phosphonate, anamine, and a quaternary ammonium; and i*, j*, k* and L*, at eachinstance, is an independently selected integer ranging from 0 to 4. Insome embodiments, each i*, j*, k* and L* is zero. In some embodiments,the total concentration of recurring unit (R^(M) _(PEKK)) and recurringunits (R^(P1) _(PEKK)), (R^(P2) _(PEKK)) and (R^(P3) _(PEKK)), is atleast 50 mol %, at least 60 mol %, at least 70 mol %, at least 80 mol %,at least 90 mol %, at least 95 mol % or at least 99 mol %, or 100 mol %,relative to the total number of moles of recurring units (R^(M) _(PEKK))and recurring units (R^(P) _(PEKK)). In some embodiments, ratio of thetotal number of moles of recurring units (R^(P1) _(PEEK)),(R^(P)2_(PEKK)), and (R^(P3) _(PEKK)) to the number of moles ofrecurring unit (R^(M) _(PEKK)) is within the ranges above described withrespect to recurring units (R^(M) _(PEKK)) and (R^(P) _(PEKK)).

As noted above, the PEKK polymers have unexpectedly lower melt viscosity(“MV”) for a given η_(inh), e.g., they exhibit a lower melt viscosityfor a the same mechanical properties. The PEKK polymers described hereincan have a ΔMV that is no more than −2 Pa·s, where

ΔMV=MV^((e))−MV and  (E1)

MV^((e)) =m _(mv)η_(inh) ^(n),  (E2)

and where MV^((e)) is the expected melt viscosity (in Pascal·seconds(“Pa·s”)) and η_(inh) is the inherent viscosity (in deciliters per gram(“dL/g”)) of the PEKK polymer. The parameters m_(mv) and n in equationE2 can be determined empirically by plotting MV vs. η_(inh) for varioustraditional PEKK polymers and fitting to the curve MV=m_(mv)η_(inh)^(n). For the PEKK polymers of interest herein where the (R^(P)_(PEKK))/(R^(M) _(PEKK)) ratio is from 55:45 (1.2:1) to 65:35 (1.86:1),MV is measured at 410° C. as decribed in the examples below andm_(mv)=1006 (Pa·s)(g/dL)^(3.9) and n=3.90, as demonstrated in theExamples below. For the PEKK polymers of interest herein where the(R^(P) _(PEKK))/(R^(M) _(PEKK)) ratio is greater than 65:35 (1.86:1) to75:25 (3.00:1), MV is measured at 380° C. as described in the examplesbelow and m_(mv)=1490 (Pa·s)(g/dL)^(3.98) andn=3.98, also asdemonstrated in the Examples below. MV and η_(inh) are measured asdescribed in the Examples below. In some embodiments, the PEKK polymerscan have ΔMV that is no more than about −3 Pa·s, no more than about −5,no more than about −10, no more than about 12, no more than about −30,no more than −40, no more than −50, or no more than −60.

The PEKK polymer can have a T_(m) from 280° C. to 370° C., from 285° C.to 360° C., or from 290° C. to 350° C. The T_(m) is measured by DSC asdescribed in the examples. The PEKK polymers can have a η_(inh) of atleast 0.40 dL/g, at least 0.50 dL/g, or at least 0.60 dL/g. Additonallyor alternatively, the PEKK polymers can have a 7η_(inh) of no more than1.50 dL/g, no more than 1.40 dL/g, or no more than 1.2 dL/g. η_(inh) ismeasured as described in the Examples below.

Additionally, as mentioned above, the PEKK polymers described hereinhave a significantly reduced residual chlorine concentration andincreased thermal stability, relative to PEKK polymers synthesized usingelectrophilic synthesis routes. Accordingly, polymer compositionsincluding the PEKK polymers can also have a significantly reducedresidual chlorine concentration. In some embodiments, a polymercomposition including the PEKK polymer can have a residual chlorineconcentration of less than about 900 parts per million by weight(“ppm”), less than about 500 ppm, less than about 400 ppm, less thanabout 300 ppm, less than about 250 ppm, less than about 100 ppm, or lessthan about 70 ppm. The residual chlorine concentration is measured asdescribed in the Examples below. With respect to increased thermalstability, the PEKK polymers of interest herein have a 1 wt. % thermaldecomposition temperature (“Td(1%)”) of at least 490° C., at least 495°C., or at least 500° C. Td(1%) is measured as described in the Examplesbelow.

Synthesis of Poly(Ether Ketone Ketone) Polymers

As mentioned above, it was found that the polymer synthesis methodsdescribed herein produces PEKK polymers having unexpectedly reduced meltviscosities. The synthesis approach involves selective control of thereactants, as well as other components of the synthesis scheme. Morespecifically, the synthesis approach involves reacting a blend ofbis(hydroxybenzoyl) benzene monomers and bis(halobenzoyl) benzenemonomers in the presence of sodium carbonate, Na₂CO₃, and a solvent,where the relative amounts of the aforementioned components are selectedto achieve PEKK polymers having unexpectedly reduced melt viscosities.

In general, the PEKK polymers of interest herein include recurring unitsformed from the polycondensation of 1,3-bis(benzoyl) monomers and1,4-bis(benzoyl) monomers having the following general formulae,respectively,

X⁵-M_(m)-X⁵, and  (13)

X⁶-M_(p)-X⁶.  (14)

where X⁵ is an —OH or halogen and X⁶ is an —OH or halogen. As usedherein, a halogen refers to any one of F, Cl, Br, and I. Preferably thehalogen is F or Cl, more preferably the halogen is F. As used herein, a1,3-bis(benzoyl) benzene monomer refers to a monomer represented byFormula (13) and 1,4-bis(benzoyl) benzene monomer refers to a monomerrepresented by Formula (14). Additionally, a bis(hydroxybenzoyl) benzenemonomer refers to a monomer represented by Formula (13) or (14) where X⁵or X⁶, respectively, is an —OH. A bis(halobenzoyl) benzene monomerrefers to a monomer represented by Formula (13) or (14) where X⁵ or X⁶,respectively, is a halogen. For example, a 1,3-bis(hydroxybenzoyl)benzene monomer refers to a monomer of Formula (13) where X⁵ is —OH. Asanother example, a 1,4-bis(halobenzoyl) benzene monomer refers to amonomer of Formula (14) where X⁶ is a halogen.

The PEKK polymers synthesis involves reacting, in a reaction mixture, ablend of bis(hydroxybenzoyl) benzene monomers and bis(halobenzoyl)benzene monomers in the presence of Na₂CO₃ and a solvent, where therelative amounts of the aforementioned components are selected accordingthe following Formulae:

Σ=(% Na₂CO₃−105)+6|% K₂CO₃−1|+0.25β7−% Monomers|−% XS_(DFDK)<6,  (EQ1)

0≤% K₂CO₃<5, and  (EQ2)

0≤% XS_(DFDK),  (EQ3)

25≤% Monomers≤44,  (EQ4)

where (a) % Na₂CO₃ is the concentration, in mol %, of Na₂CO₃, relativeto the number of moles of bis(hydroxybenzoyl) benzene monomers; (b) %K₂CO₃ is the concentration, in mol %, of potassium carbonate, K₂CO₃,relative to the number of moles of bis(hydroxybenzoyl) benzene monomers;(c) % Monomers is the total concentration, in wt. %, ofbis(hydroxybenzoyl) benzene monomers and bis(halobenzoyl) benzenemonomers relative to the total weight of the bis(hydroxybenzoyl) benzenemonomers, bis(halobenzoyl) benzene monomers and solvent; and (d) %XS_(DFDK) is the concentration, in mol %, of bis(halobenzoyl) benzenemonomers in excess of an equimolar concentration, relative to theconcentration of bis(hydroxybenzoyl) benzene monomers. For ease ofreference, Na₂CO₃, K₂CO₃, bis(hydroxybenzoyl) benzene monomers,bis(halobenzoyl) benzene monomers and solvent are collective referred toas “reaction components.” In general, for the PEKK polymers of interestherein, Σ<6.0, preferably Σ<5.5, more preferably Σ<5.0. For PEKKpolymers having a (R^(P) _(PEKK))/(R^(M) _(PEKK)) ratio of more than65/35 (1.86:1) to 75/25 (3.00:1), Σ<6.0, preferably Σ<5.5, morepreferably Σ<5.0. For PEKK polymers having a (R^(P) _(PEKK))/(R^(M)_(PEKK)) ratio of 55/45(1.22:1) to 65/35 (1.87:1), Σ<2.0, preferablyΣ<1.5, more preferably Σ<1.0.

With respect to % Na₂CO₃ and % K₂CO₃, in some embodiments, % Na₂CO₃+%K₂CO₃<106.0%. % Na₂CO₃+K₂CO₃ is preferably at least 95%, more preferablyat least 100%, more preferably at least 102%. Preferably, the Na₂CO₃meets the particle size distribution requirements as detailed in U.S.Pat. No. 9,175,136, to Louis, filed Oct. 23, 2009 and incorporatedherein by reference.

With respect to % XS_(DFDK), it reflects the quantity ofbis(halobenzoyl) benzene monomers in excess of an equimolar quantity ofbis(hydroxybenzoyl) benzene monomers. As noted above, each recurringunit (R^(M) _(PEKK)) and (R^(P) _(PEKK)) is formed from thepolycondensation of a bis(hydroxybenzoyl) benzene monomer and abis(halohydroxy) benzene monomer, such that the number of moles ofbis(hydroxybenzoyl) benzene monomers and bis(halohydroxy) benzenemonomers is equimolar. Accordingly, in embodiments in which %XS_(DFDK)>0, the monomer blend includes more moles of bis(halobenzoyl)benzene monomers, relative to the number of moles of bis(hydroxybenzoyl)benzene monomers. In some such embodiments, % XS_(DFDK) is from 0.1 mol% to 10.0 mol %, preferably from 0.3 mol % to 5.0 mol %, more preferablyfrom 0.5 to 3.0 mol %.

With respect to the solvent, it can include, but is not limited to,diphenyl sulfone, dibenzothiophene dioxide, benzophenone or combinationsof any one or more thereof. Preferably, the solvent includes diphenylsulfone. More preferably, the solvent includes at least 90 wt. %, atleast 95 wt. %, at least 98 wt. % or at least 99 wt. % diphenyl sulfone.In some embodiments, the diphenyl sulfone is used in the synthesismethod described herein includes limited amounts of impurities, asdetailed in U.S. Pat. No. 9,133,111, to Louis et al., filed Apr. 7, 2014and incorporated herein by reference.

With respect to the relative concentration of bis(hydroxybenzoyl)benzene monomers and bis(halobenzoyl) benzene monomers, it is noted thateach recurring unit of (R^(M) _(PEKK)) and recurring units (R^(P)_(PEKK)) is formed from the polycondensation of a bis(hydroxybenzoyl)benzene monomer (a 1,3-bis(hydroxybenzoyl) benzene monomer or1,4-bis(hydroxybenzoyl) benzene monomer) and a bis(halobenzoyl) benzenemonomer (a 1,3-bis(halobenzoyl) benzene monomer or 1,4-bis(halobenzoyl)benzene monomer). Accordingly, the ratio of the total amount ofbis(hydroxybenzoyl) benzene monomers to the total amount ofbis(halobenzoyl) benzene monomers used in the synthesis reaction to formthe recurring units (R^(M) _(PEKK)) and (R^(P) _(PEKK)) is substantiallyequimolar. As used herein, substantially equimolar means within 10% ofequimolar, preferably 5% of equimolar, most preferably within 3% ofequimolar. For example, the ratio of the number of moles ofbis(hydroxybenzoyl) benzene monomer to the number of moles of thebis(halobenzoyl) benzene monomer is from about 0.9:1 to about 1:0.9,more preferably 0.95:1 to 1:0.95, most preferably from about 0.97:1 toabout 1:0.97, and most preferably between 0.97:1 and 1.00:1.

More specifically, each recurring unit (R^(M) _(PEKK)) is formed fromthe polycondensation of two, distinct 1,3-bis(benzoyl) benzene monomers;or from the polycondensation of a 1,3-bis(benzoyl) benzene monomer and a1,4-bis(benzoyl) benzene monomer. Analogously, each recurring unit(R^(P) _(PEKK)) is formed from the polycondensation of two, distinct1,4-bis(benzoyl) benzene monomers; or from the polycondensation of a1,3-bis(benzoyl) benzene monomer and a 1,4-bis(benzoyl) benzene monomer.For example, the polycondensation of a monomer according to the formulaX⁵-M_(m)-X⁵ (1,3-bis(benzoyl) benzene) with a monomer according to theformula X⁶-M_(p)-X⁶ (1,4-bis(benzoyl) benzene), forms recurring units(R^(P) _(PEKK)) and (R^(M) _(PEKK)), where X⁵ is an —OH or halogen andX⁶ is a halogen if X⁵ is an —OH and X⁶ is an —OH if X⁵ is a halogen. Asanother example, the polycondensation of a monomer according to theformula X⁵-M_(m)-X⁵ (1,3-bis(benzoyl) benzene) with a monomer accordingto the formula X⁷-M*_(m)-X⁷ (1,3-bis(benzoyl) benzene) forms recurringunits (R^(M) _(PEKK)), where M*_(m) is represented by a Formula (13),the same or distinct from M_(m), and where X⁵ is an —OH or halogen andX⁷ is a halogen if X⁵ is an —OH and X⁷ is an —OH if X⁵ is a halogen. Asyet another example, the polycondensation of a monomer according to theformula X⁶-M_(p)-X⁶ (1,4-bis(benzoyl) benzene) with a monomer accordingto the formula X⁸-M*_(p)-X⁸(1,4-bis(benzoyl) benzene), forms recurringunits (R^(P) _(PEKK)), where M*_(p) is represented by a Formula (14),the same or distinct from M_(p), and where X⁶ is an —OH or halogen andX⁸ is a halogen if X⁶ is an —OH and X⁸ is an OH if X⁶ is a halogen.

As noted above, the PEKK polymers of interest herein have a (R^(P)_(PEKK))/(R^(M) _(PEKK)) ratio of from 55/45 to 75/25. Accordingly, theratio of the number of moles of 1,4-bis(benzoyl) benzene monomers to thenumber of moles of 1,3-bis(benzoyl) benzene monomers (“1,4/1,3 ratio”)in the blend of bis(hydroxybenzoyl) benzene monomers andbis(halobenzoyl) benzene monomer is from 55/45 to 75/25. As long as theaforementioned 1,4/1,3 ratio is satisfied, the relative amount ofbis(hydroxybenzoyl) benzene monomers and bis(halobenzoyl) benzenemonomers that are 1,4-bis(benzoyl) benzene and 1,3-bis(benzoyl) benzenemonomers is not particularly limited. In some embodiments, at least 90mol %, at least 95 mol % or at least 99 mol % of the 1,3-bis(benzoyl)benzene monomers are either 1,3-bis(hydroxybenzoyl) benzene monomers or1,3-bis(halobenzoyl) benzene monomers, relative to the number of molesof recurring units (R^(M) _(PEKK)) in the PEKK polymer.

Significantly, the prescribed concentrations of the reaction components,as well as other concentrations of the reaction components describedherein, are relative to the quantities of the reaction components usedto form recurring units (R^(M) _(PEKK)) and (R^(P) _(PEKK)). Put anotherway, one or more of the reaction components can be independentlyincorporated into the reaction mixture at distinct points during thereacting. In some embodiments, the reaction mixture contains each of thereaction components in the quantities prescribed by Formulae (EQ1)-(EQ4)(“prescribed quantity”) and the prescribed quantities ofbis(hydroxybenzoyl) benzene monomers and bis(halobenzoyl) benzenemonomers are reacted simultaneously. For example, in one suchembodiment, the reaction mixture contains, simultaneously, Na₂CO₃,K₂CO₃, bis(hydroxybenzoyl) benzene monomers, bis(halobenzoyl) benzenemonomers and solvent in their prescribed quantities prior to thereacting and the corresponding monomers are reacted therein. Inalternate embodiments, one or more of the reaction components can beadded to the reaction mixture at different points prior to or during thereacting. In some such embodiments, a portion of the prescribed quantityof one or more of the reaction components is added to the reactionmixture prior to the reacting and the remainder of the prescribedquantity of the one or more components is added to the reaction mixtureduring the reacting. In a preferred embodiment, at least 90 mol %, atleast 95, or at least 99 mol % of the 1,3-bis(benzoyl) benzene monomersforming recurring units (R^(M) _(PEK)) are added to the reaction mixtureeither prior to the reacting or during the reaction and at least 90 mol%, at least 95, or at least 99 mol % of the 1,4-bis(benzoyl) benzenemonomers forming the remaining recurring units (R^(P) _(PEKK)) are addedto the reaction mixture during the reacting or prior to the reacting,respectively. In another preferred embodiment, the prescribed quantityof solvent is present in the reaction mixture prior to the reacting. Insome embodiments, the prescribed quantity of Na₂CO₃ and K₂CO₃ can beadded to the reaction mixture either prior to the reacting or during thefirst reaction. Based upon the description herein, a person of ordinaryskill in the art will recognize additional methods of the adding theindividual reaction components to the reaction mixture.

The reacting can include a first heating in which the reaction mixtureis heated to maintain its temperature within a first temperature rangeof from 180° C. to 270° C. In some embodiments, the first heating caninclude maintaining the temperature of the reaction mixture within thefirst temperature range for a first period of time. The first period oftime can be from 5 minutes (“min.”) to 300 min., from 7 min. to 240 min.or from 10 min. to 180 min or from 15 min to 120 min. As noted above,one or more of the reaction components can be independently added to thereaction mixture at distinct points during the reacting. In someembodiments, each of reaction components, in their prescribedquantities, is added to the reaction mixture prior to the first heating.In alternate embodiments, at least one or more of the reactioncomponents is added to the reaction mixture during the first heating andthe remainder of the reaction components are added to the reactionmixture prior to the first heating. In some such embodiments, theprescribed quantity of the one or more reaction components is added tothe reaction mixture during the first heating (e.g. the full amount ofthe one or more reaction components). In alternative such embodiments,only a portion of the prescribed quantity of the one or more reactioncomponents is added to the reaction mixture during the first heating andthe remaining portion is added to the reaction mixture prior to thefirst heating. In general, each reaction component is present in thereaction mixture in its prescribed quantity prior to the end of thefirst heating. In such embodiments, the first time period is relative tothe point in time at which the prescribed quantity of each reactioncomponent has been added to the reaction mixture. In a preferredembodiment, at least 90 mol %, at least 95, or at least 99 mol % of the1,3-bis(benzoyl) benzene monomers forming recurring units (R^(M) _(PEK))are added either prior to the first heating or during the first heatingand wherein at least 90 mol %, at least 95, or at least 99 mol % of the1,4-bis(benzoyl) benzene monomers forming the remaining 1,4-bis(benzoyl)benzene monomers are added during the first heating or prior to thefirst heating, respectively.

In some embodiments, the reacting further includes a second heating,subsequent to the first heating, in which the reaction mixture is heatedto maintain its temperature within a second temperature range that isfrom 300° C. to 340° C. In some such embodiments, the reaction mixturecan be maintained with the second temperature range for a second periodof time. The second period of time period can be from 0 to 240 min.,from 0 to 180 min., or more 0 to 120 min. In some embodiments, thesecond heating further includes adding an end-capping agent to thereaction mixture. The end-capping agent controls the molecular weight ofthe PEKK polymer by terminating the polymerization reaction at aselected point during polymerization.

In such embodiments, the second heating includes the second addition.Desirable end-capping agents include those represented by the followingformula:

where g is —C(O)—Ar or S(O2)-Ar, and Ar is an arylene group. In someembodiments, the end-capping agent is an excess of a bis(halobenzoyl)benzene monomer (1,3-bis(halobenzoyl) benzene monomer or1,4-bis(halobenzoyl) benzene monomer) used to form recurring units(R^(M) _(PEKK)) or recurring units (R^(P) _(PEKK)) of the PEKK polymer.As used herein, and excess refers to amount of the 1,3-bis(halobenzoyl)benzene monomer or 1,4-bis(halobenzoyl) benzene monomer above the amountthat would bring the total amount of the respective monomer added to thereaction mixture to at least 1.04 times an equimolar amount to thebis(hydroxybenzoyl) benzene monomer, preferably at least 1.05, morepreferably at least 1.07. For clarity, in embodiments, in which theend-capping agent is a bis(halobenzoyl) benzene monomer used to formused to form recurring units (R^(M) _(PEKK)) or recurring units (R^(P)_(PEKK)), the amount of end-capping agent is not included in the %XS_(DFDK).

In some embodiments of the method for forming a PEKK polymer,bis(hydroxybenzoyl) benzene monomers and bis(halobenzoyl) benzenemonomers collectively include at least one first 1,3-bis(benzoyl)benzene monomer, at least one first 1,4-bis(benzoyl) benzene monomer, atleast one second 1,4-bis(benzoyl) benzene monomer, and at least onethird 1,4-bis(benzoyl) benzene monomer, where each 1,3-bis(benzoyl)benzene monomer is represented by a formula according to Formula (13)and each 1,4-bis(benzoyl) benzene monomer is represented by a formulaaccording to Formula (14). In some such embodiments, one of the at leastone first 1,3-bis(benzoyl) benzene monomer, one of the at least onefirst 1,4-bis(benzoyl) benzene monomer, one of the at least one second1,4-bis(benzoyl) benzene monomer, and one of the the at least one third1,4-bis(benzoyl) benzene monomer are represented by the followingformulae, respectively:

X¹-M¹*_(m)-X¹,  (16)

X²-M¹*_(p)-X²,  (17)

X³-M²*_(p)-X³,  (18)

X⁴-M³*_(p)-X⁴, and  (19)

wherein X¹ is —OH or a halogen; X² is a halogen if X¹ is an —OH and X²is an —OH if X¹ is a halogen; X³ is an —OH or a halogen; and X⁴ is anhalogen if X³ is an —OH and X⁴ is an —OH if X³ is a halogen. In somesuch embodiments, monomers X¹-M*¹ _(m)-X¹ and X²-M*¹ _(p)-X²polycondense to form recurring units (R^(M1) _(PEKK)) and (R^(P1)_(PEKK)), respectively, and monomers X³M*_(p)-X³ and X⁴-M*_(p)-X⁴polycondense to form recurring units (R^(P2) _(PEKK)), and (R^(P3)_(PEKK)), respectively. In some such embodiments X¹ and X³ are —OH. Insome embodiments, each i*, j*, k* and L* are zero, such that recurringunits (R^(P1) _(PEKK)), (R^(P2) _(PEKK)) and (R^(P3) _(PEKK)) areidentical.

Polymer Compositions, Shaped Articles, and Applications

The PEKK polymers described herein can be desirably used in polymercompositions and incorporated into shaped articles, including but notlimited to mobile electronic devices, medical devices, and compositematerials. Furthermore, the PEKK polymers, or compositions thereof, canalso be desirably used in additive manufacturing application settings.

Polymer compositions including the PEKK polymers (“PEKK polymercompositions”) can include a reinforcing filler. Reinforcing fillersinclude fibrous fillers and particulate fillers, distinct from thepigments described below. Particulate filers include mineral fillersincluding, but not limited to, talc, mica, kaolin, calcium carbonate,calcium silicate, and magnesium carbonate. Fibrous fillers include, butare not limited to, glass fiber, carbon fiber, synthetic polymericfiber, aramid fiber, aluminum fiber, titanium fiber, magnesium fiber,boron carbide fiber, rock wool fiber, steel fiber, wollastonite.Preferably the reinforcing fillers is selected from mica, kaolin,calcium silicate, magnesium carbonate, glass fiber, carbon fiber,wollastonite, and any combination of one or more thereof.

Preferably, the filler is a fibrous filler. A particular class offibrous fillers consists of whiskers, i.e. single crystal fibers madefrom various raw materials, such as Al₂O₃, SiC, BC, Fe and Ni. In oneembodiment, the reinforcing filler is selected from wollastonite andglass fiber. Among fibrous fillers, glass fibers are preferred; theyinclude chopped strand A-, E-, C, D-, S-, T- and R-glass fibers, asdescribed in chapter 5.2.3, p. 43-48 of Additives for Plastics Handbook,2nd edition, John Murphy.

When the glass fibers has a circular cross-section, they preferably havean average glass fiber diameter of 3 to 30 μm and particularly preferredof 5 to 12 μm. Different sorts of glass fibers with a circularcross-section are available on the market depending on the type of theglass they are made of. One may notably cite glass fibers made from E-or S-glass.

In some embodiments, the reinforcing filler includes carbon fiber. Asused herein, the term “carbon fiber” is intended to include graphitized,partially graphitized and ungraphitized carbon reinforcing fibers or amixture thereof. Carbon fibers can advantageously be obtained by heattreatment and pyrolysis of different polymer precursors such as, forexample, rayon, polyacrylonitrile (PAN), aromatic polyamide or phenolicresin; carbon fibers may also be obtained from pitchy materials. Theterm “graphite fiber” intends to denote carbon fibers obtained by hightemperature pyrolysis (over 2000° C.) of carbon fibers, wherein thecarbon atoms place in a way similar to the graphite structure. Carbonfibers are preferably selected from PAN-based carbon fibers, pitch basedcarbon fibers, graphite fibers, and any combination of one or morethereof.

The weight of the reinforcing filler is preferably below 80% wt., morepreferably below 70% wt., even more preferably below 65% wt., based onthe total weight of the composition.

In some embodiments, the PEKK polymer compositions can include, inaddition or alternatively to the reinforcing filler one or moreadditional ingredients selected from the group consisting of (i)colorants (e.g. a dye); (ii) pigments (e.g., titanium dioxide, zincsulfide and zinc oxide); (iii) light stabilizers (e.g. UV stabilizers);(iv) heat stabilizers; (v) antioxidants (e.g. organic phosphites andphosphonites); (vi) acid scavengers (vii) processing aids (viii)nucleating agents (ix) plasticizer, internal lubricants, and externallubricants; (x) flame retardants (xi) smoke-suppressing agents (x)anti-static agents (xi) anti-blocking agents (xii) conductivityadditives (e.g. carbon black and carbon nanofibrils) (xiii)plasticizers; (xiv) flow modifiers; (xv) extenders; (xvi) metaldeactivators and any combination of one or more thereof. In someembodiments, the total concentration of additional ingredients is below20%, preferably below 10%, more preferably below 5% and even morepreferably below 2%, based upon the total weight of the polymercomposition.

In some embodiments, the composition comprises the PEKK polymer incombination with one or more than one additional polymeric components,such as polyarylether polymers different from PEKK polymer, including,but not limited to, poly(ether ether ketone) (“PEEK”) polymers,poly(ether ketone) (“PEK”) polymers, sulfone polymers, and polyarylsulphide polymers. According to other embodiments, the PEKK polymer, asabove detailed, is the only polymeric component in PEKK polymercomposition. The expression ‘polymeric components’ is to be understoodaccording to its usual meaning, i.e. encompassing compoundscharacterized by repeated linked units, having typically a molecularweight of 2,000 g/mol or more.

As noted above, the PEKK polymers synthesized as described herein havesignificantly reduced residual chlorine concentration, relative tocorresponding PEKK polymer synthesized using an electrophilic route. Thepolymer compositions including the PEKK polymers synthesized asdescribed herein can have a residual chlorine concentration of less than900 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, lessthan 250 ppm, less than 100 ppm, or less than 70 ppm.

The PEKK polymer compositions can be prepared by a variety of methodsinvolving intimate admixing of the PEKK polymer, optionally thereinforcing filler and optionally the above described additionalingredient desired in the PEKK polymer composition, for example by dryblending, suspension or slurry mixing, solution mixing, melt mixing or acombination of dry blending and melt mixing.

Typically, the dry blending of PEKK polymer, as detailed above,preferably in powder state, optionally the reinforcing filler andoptionally additional ingredients is carried out by using high intensitymixers, such as notably Henschel-type mixers and ribbon mixers so as toobtain a physical mixture, in particular a powder mixture of the atleast one PEKK polymer, optionally the reinforcing filler and optionallyadditional ingredients. Alternatively, the intimate admixing of the PEKKpolymer, optionally the reinforcing filler and optionally additionalingredients desired in the PEKK polymer composition, is carried out bytumble blending based on a single axis or multi-axis rotating mechanismso as to obtain a physical mixture.

Alternatively, the slurry mixing of the PEKK polymer, optionally thereinforcing filler and optionally additional ingredients is carried outby first slurrying the PEKK polymer, as above detailed, in powder form,optionally the reinforcing filler and optionally additional ingredientsusing an agitator in an appropriate liquid such as for example methanol,followed by filtering the liquid away, so as to obtain a powder mixtureof the at least one PEKK polymer, optionally the reinforcing filler andoptionally additional ingredients.

In another embodiment, the solution mixing of the PEKK polymer, asdetailed above, optionally the reinforcing filler and optionallyadditional ingredients using an agitator in an appropriate solvent orsolvent blends such as for example diphenyl sulfone, benzophenone,4-chlorophenol, 2-chlorophenol, meta-cresol. Diphenyl sulfone is mostpreferred.

Following the physical mixing step by one of the aforementionedtechniques, the physical mixture, in particular the obtained powdermixture, of the at least one PEKK polymer, optionally the reinforcingfiller and optionally additional ingredients is typically meltfabricated by known methods in the art including notably meltfabrication processes such as compression molding, injection molding,extrusion and the like, to provide shaped articles.

So obtained physical mixture, in particular the obtained powder mixturecan comprise the PEKK polymer, the reinforcing filler, as detailedabove, and optionally, other ingredients in the weight ratios as abovedetailed, or can be a concentrated mixture to be used as masterbatch anddiluted in further amounts of the PEKK polymer, as above detailed, thereinforcing filler, as detailed above, and optionally, other ingredientsin subsequent processing steps. For example, the obtained physicalmixture can be extruded into a stock shape like a slab or rod from whicha final part can be machined. Alternatively, the physical mixture can becompression molded into a finished part or into a stock shape from whicha finished part can be machined.

It is also possible to manufacture the composition of the invention byfurther melt compounding the powder mixture as above described. As said,melt compounding can be effected on the powder mixture as abovedetailed, or directly on the PEKK polymer, as above detailed, thereinforcing filler, as detailed above, and optionally, otheringredients. Conventional melt compounding devices, such as co-rotatingand counter-rotating extruders, single screw extruders, co-kneaders,disc-pack processors and various other types of extrusion equipment canbe used. Preferably, extruders, more preferably twin screw extruders canbe used.

If desired, the design of the compounding screw, e.g. flight pitch andwidth, clearance, length as well as operating conditions will beadvantageously chosen so that sufficient heat and mechanical energy isprovided to advantageously fully melt the powder mixture or theingredients as above detailed and advantageously obtain a homogeneousdistribution of the different ingredients. Provided that optimum mixingis achieved between the bulk polymer and filler contents, it isadvantageously possible to obtain strand extrudates of the PEKK polymercomposition of the invention. Strand extrudates of the PEKK polymercomposition can be chopped by means e.g. of a rotating cutting knifeafter some cooling time on a conveyer with water spray. Thus, forexample a PEKK polymer composition which may be present in the form ofpellets or beads can then be further used for the manufacture of shapedarticles, notably of different shape and size.

The PEKK polymer compositions (or PEKK polymer) can be desirablyincorporated into shaped articles. The shaped articles can be made fromthe PEKK polymer composition using any suitable melt-processing meltprocessing technique including, but not limited to, extrusion molding,injection molding, and compression molding. In some embodiments, theshaped articles are under the form of substantially bidimensionalarticles. Bidimensional articles include parts in which one dimension(thickness or height) is significantly less than the other twocharacterizing dimensions (width and length), for example, films andsheets. In some embodiments, the shaped article can be a coating. Insome embodiments, the shaped articles are three-dimensional parts.Three-dimensional parts include parts that substantially extend in thethree dimensions of space in similar manner, including under the form ofcomplex geometries parts (e.g., concave or convex sections, possiblyincluding undercuts, inserts, and the like).

In some embodiments, the shaped article is a component of a mobileelectronic device. As used herein, a “mobile electronic device” refersto an electronic device that is transported and used in variouslocations. A mobile electronic device can include, but is not limitedto, a mobile phone, a personal digital assistant (“PDA”), a laptopcomputer, a tablet computer, a wearable computing device (e.g., a smartwatch and smart glasses), a camera, a portable audio player, a portableradio, a global position system receiver, and portable game console.

In some embodiments, at least a portion of a component of a mobileelectronic device can be exposed to the external environment of themobile electronic device (e.g., at least a portion of the component isin contact with the environment external to the mobile electronicdevice). For example, at least a portion of the component can form atleast a portion of the external housing of the mobile electronic device.In some such embodiments, the component can be a full or partial “frame”around the periphery of the mobile electronic device, a beam in the formof a lattice work, or a combination thereof. As another example, atleast a portion of the component can form at least a portion of an inputdevice. In some such embodiments, a button of the electronic device caninclude the component. In some embodiments, the component can be fullyenclosed by the electronic device (e.g., the component is not visiblefrom an observation point external to the mobile electronic device).

In some embodiments, the PEKK polymers can be desirably incorporatedinto composites. In such embodiments, long fibers are solution,suspension or melt-impregnated with the PEKK polymer to form thecomposite. The long fibers generally have a length of at least 10microns (“μm”). The fibers can be glass fibers or carbon fibers. In someembodiments, the composite can form a tape or woven fabric.

In some embodiments, the component can be of a mounting component withmounting holes or other fastening device, including but not limited to,a snap fit connector between itself and another component of the mobileelectronic device, including but not limited to, a circuit board, amicrophone, a speaker, a display, a battery, a cover, a housing, anelectrical or electronic connector, a hinge, a radio antenna, a switch,or a switchpad. In some embodiments, the mobile electronic device can beat least a portion of an input device.

The components of the mobile electronic device can be fabricated fromthe PEKK polymer compositions using methods well known in the art. Forexample, the mobile electronic device components can be fabricated bymethods including, but not limited to, injection molding, blow moldingor extrusion molding. In some embodiments, PEKK polymer composition canbe formed into pellets (e.g., having a substantially cylindrical bodybetween two ends) by methods known in the art including, but not limitedto, injection molding. In some such embodiments, mobile electronicdevice components can be fabricated from the pellets.

Additionally, due to the improved processability (e.g. lower MV) andhigher thermal stability, the PEKK polymers described herein can bedesirably used in 3D printing (also known as additive manufacturing)fabrication technique such as fused filament fabrication (FFF) orselective laser sintering (SLS). Additive manufacturing involves theprocess of joining materials to make articles from 3D model data. Thearticle is generally formed using layer by layer deposition.Commercially available 3D printing fabrication equipments of the FFFtype include, as an example, the equipment manufactured by Stratasys,Inc. and sold under the Fortus® trademark. Examples of SLS based 3Dprinting equipment are available from EOS corporation such as the onessold under the trade name EOSINT®. In such embodiments, an article canbe formed by 3D printing the PEKK polymer (or PEKK polymer composition).

In some embodiments, the shaped articles described herein are medicaldevices or components of medical devices. As used herein, a “medicaldevice” is an article, instrument, apparatus or machine that is used inthe prevention, diagnosis, or treatment of illness or disease, or fordetecting, measuring, restoring, correcting, or modifying the structureor function of a human or animal body.

Material selection is critical for medical devices, particularly ininstances where the material is implanted in, or comes into contactwith, the body. There is a continued need for medical device materialsthat meet the particular requirements of the medical device in itsapplication setting (e.g. wear resistance), and also reduce or preventundesirable interactions with the body, such as, for example, theleaching of chemicals from the medical device into the body.

The PEKK polymers described herein may be particularly suitable for usein medical devices, for example, because of their higher purity asreflected in their reduced chlorine and metals content.

Medical devices can generally include surgical devices, non-surgicaldevices, prosthetic devices, implants, etc.

In some embodiments, the medical device including the PEKK polymersdescribed herein is an implantable medical device (IMD). IMDs aremedical devices designed to replace a missing biological structure,support a damaged biological structure, or enhance an existingbiological structure in the body. Examples of IMDs include cranialimplants such as craniomaxillofacial implants, spinal implants such asspinal cages and spinal disks, finger and toe implants, kneereplacements, hip replacements such as acetabular caps, stents, heartvalves, pacemakers, and hardware such as bone screws and plates. Themedical devices may also include dental devices such as removable fulland partial denture frames, crowns, bridges, artificial teeth, andimplant bars.

EXAMPLES

The following Examples demonstrate the synthesis of PEKK, therheological and thermal properties of the synthesized PEKK polymers.

The following materials and measurement methods were used, referenced inthe individual examples below.

Poly(Ether Ether Ketone) Polymers

In the Examples, some of the PEKK polymers were commercially obtained,while other PEKK polymers were synthesized. Commercial aromatic PEKKpolymers were obtained from Solvay S.A. (Brussels, Belgium) under thetrade names Cypek® FC and Cypek® DS, which present different levels ofcrystallinity.

Synthesized PEKK polymers were synthesized from the following monomers,as explained in further detail in each example below:1,4-bis(4′-fluorobenzoyl); 1,3-bis(4′-fluorobenzoyl)benzene;1,4-bis(4′-hydroxybenzoyl)benzene; and1,3-bis(4′-hydroxybenzoyl)benzene. 1,4-bis(4′-fluorobenzoyl)benzene wasprepared by Friedel-Crafts acylation of fluorobenzene according toexample 1 of U.S. Pat. No. 5,300,693 to Gilb et al. (filed Nov. 25, 1992and incorporated herein by reference), purified by recrystallization inchlorobenzene to reach a GC purity of 99.9%.1,3-bis(4′-fluorobenzoyl)benzene was procured from 3B Corp, USA andpurified by recrystallization in chlorobenzene to reach a GC purity of99.9%. 1,4-bis(4′-hydroxybenzoyl)benzene and1,3-bis(4′-hydroxybenzoyl)benzene were produced by hydrolysis of1,4-bis(4′-fluorobenzoyl)benzene and 1,3-bis(4′-fluorobenzoyl)benzene,respectively following the procedure described in example 1 of U.S. Pat.No. 5,250,738 to Hackenbruch et al. (filed Feb. 24, 1992 andincorporated herein by reference), and purified by recrystallization inDMF/ethanol to reach a GC purity of 99.0%. Diphenyl sulfone (polymergrade) was commercial obtained from Proviron (99.8% pure). Othercomponents used in the PEKK syntheses were sodium carbonate, light sodaash SodaSolvay L® and commercially obtained from Solvay S.A. (France),and potassium carbonate (d₉₀<45 μm), commercially obtained from ArmandProducts Company (USA). The sodium carbonate, light soda ash andpotassium carbonate were dried before use. Lithium chloride (anhydrouspowder) was also used in the PEKK syntheses and was commerciallyobtained from Acros Organics (Geel, Belgium).

Analytic Methods

The PEKK polymers were characterized using the following analyticalmethods. Inherent viscosity (“η_(inh)”) was measured following ASTMD2857 at 30° C. on 0.5 wt./vol. % solutions in concentrated H₂SO₄ (96wt. % minimum) using a Cannon-Fenske capillary, size 200.

The determination of residual chlorine concentration in PEKK wasmeasured as follows. Using forceps, a clean, dry combustion boat wasplaced onto a microbalance, and the balance was zeroed. One to fivemilligrams (“mg”) of polymer sample was weighed into a combustion boatand weight was recorded to 0.001 mg. The combustion boat and sample wereplaced in the introduction port of a ThermoGLAS 1200 Total OrganicHalogen Analyzer, and the port was capped. The sample weight was enteredinto the sample weight field on the instrument computer. The sampleanalysis cycle was then started. The sample was burned in a mixture ofargon and oxygen and the combustion products were passed throughconcentrated sulfuric acid scrubber to remove moisture and byproduct.Hydrogen chloride and oxychlorides from the combustion process wereabsorbed into the cell acetic acid solution from the gas stream.Chloride entered the cell was titrated with silver ions generatedcoulometrically. Percent chlorine in the sample was calculated from theintegrated current and the sample weight.

Td(1%) was measured by thermal gravimetric analysis (“TGA”) according tothe ASTM D3850. TGA was performed on a TA Instruments TGA Q500 from 30°C. to 800° C. under nitrogen (60 mL/min) at a heating rate of 10°C./minute.

The Tg (mid-point), Tm and ΔH_(f) of the PEKK polymers were measured asfollows: Tg (mid-point) and Tm were determined on the 2nd heat scan indifferential scanning calorimeter (DSC) according to ASTM D3418-03,E1356-03, E793-06, E794-06. Details of the procedure as used in thisinvention are as follows: a TA Instruments DSC Q20 was used withnitrogen as carrier gas (99.998% purity, 50 mL/min). Temperature andheat flow calibrations were done using indium. Sample size was 5 to 7mg. The weight was recorded±0.01 mg. The heat cycles were: 1st heatcycle: 30.00° C. to 400.00° C. at 20.00° C./min, isothermal at 400.00°C. for 1 min; 1st cool cycle: 400.00° C. to 30.00° C. at 20.00° C./min,isothermal for 1 min; and 2nd heat cycle: 30.00° C. to 400.00° C. at20.00° C./min, isothermal at 400.00° C. for 1 min. The meltingtemperature Tm was determined as the peak temperature of the meltingendotherm on the 2nd heat scan. The enthalpy of fusion was determined onthe 2nd heat scan. The enthalpy of fusion was determined on the 2nd heatscan and was taken as the area over a linear baseline drawn from abovethe Tg to a temperature above end of the endotherm.

The melt viscosity (“MV”) was measured using a capillary rheometeraccording to ASTM D3835. Readings were taken after 10 minute dwell timeat 410° C. or at 380° C. as indicated in the tables and a shear rate of46.3 s-1 using a die with the following characteristics: diameter=1.016mm, length=20.32 mm, cone angle=120°.

Tensile properties were measured as follows. For examples CE1 to E8: A102 mm×102 mm×3.2 mm plaque was prepared from the polymer by compressionmolding under the following conditions: 1) preheat at 343° C.; 2) 343°C./15 minutes, 2000 kg-f, 3) 343° C./2 minutes, 2700 kg-f; and 4) cooldown to 30° C. over 40 minutes, 2000 kg-f. For examples CE9 to E26 thesame molding program was used except that the temperature for steps 1 to3 was set at 377° C. The 102 mm×102 mm×3.2 mm compression molded plaqueswere machined into Type V ASTM tensile specimens and these specimens ofthe various polymer compositions were subjected to tensile testingaccording to ASTM method D638 at 0.05 inch/minute room temperature (i.e.23° C.) on 5 specimens.

In the examples below, the T/I ratio refers to the ratio of the numberof moles of recurring unit (R^(P) _(PEKK)) to the number of moles ofrecurring unit (R^(M) _(PEKK)).

Comparative Example 1: Analysis of PEKK Synthesized by ElectrophilicSynthesis Route

The following example demonstrates the analysis of PEKK synthesizedusing an electrophilic synthesis route. Cypek® DS was analyzed asdescribed above, and the results are displayed in Tables 1 and 2.

Comparative Example 2a: Synthesis and Analysis of PEKK with 60/40 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route, according to Chinese patentapplication publication number 1974631 to Zhou and filed Nov. 21, 2006(“the CN'631 application”).

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 249.93 g of diphenyl sulfone, 39.790 g of1,4-bis(4′-hydroxybenzoyl)benzene, 8.057 g of1,4-bis(4′-fluorobenzoyl)benzene, 32.230 g of1,3-bis(4′-fluorobenzoyl)benzene and 13.646 g of Na₂CO₃. The flaskcontent was evacuated under vacuum and then filled with high puritynitrogen (containing less than 10 ppm 02). The reaction mixture was thenplaced under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated to 120° C., then from 120° C. to 160° C.at 2° C./min. The mixture was then held at 160° C. for 1 h, heated up to210° C. at 5° C./min and held at 210° C. for 1 h. The mixture was thenheated up to 250° C. at 5° C./min and held at 250° C. for 1 h. Themixture was then heated up to 290° C. at 10° C./min and held at 290° C.for 2 h. The mixture was heated up to 310° C. at 10° C./min and held at310° C. for 3 h. The reactor content was then poured from the reactorinto a satinless steell pan and cooled. The solid was broken up andground in an attrition mill through a 2 mm screen. Diphenyl sulfone andsalts were extracted from the mixture with acetone and water at pHbetween 1 and 12. The powder was then removed from the reactor and driedat 120° C. under vacuum for 12 hours yielding 68 g of anoff-white/yellow powder. The PEKK polymer had a T/I of 60/40 and can berepresented as follows:

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

Comparative Example 2b: Synthesis and Analysis of PEKK with 60/40 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route, according to the CN'631application.

The same procedure as for Comparative Example 2a was followed but thereaction time at 310° C. was shortened to 2 hours to obtain a lowermolecular weight polymer. The PEKK polymer was analyzed as describedabove. The synthesis parameters and results of the analysis aredisplayed in Tables 1 to 3.

Comparative Example 3: Synthesis and Analysis of PEKK with 60/40 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 107.38 g of diphenyl sulfone, 26.739 g of1,3-bis(4′-hydroxybenzoyl)benzene, 6.685 g of1,4-bis(4′-hydroxybenzoyl)benzene, 11.541 g of Na₂CO₃ and 0.073 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 200° C., then held at 200° C.for 45 minutes. At 200° C., 33.165 g of 1,4-bis(4′-fluorobenzoyl)benzenewas added via a powder dispenser to the reaction mixture over 30minutes. At the end of the addition, the reaction mixture was heated to320° C. at 1° C./minute. After 96 minutes at 320° C., 3.832 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reaction mixturewhile keeping a nitrogen purge on the reactor. After 5 minutes, 0.445 gof lithium chloride were added to the reaction mixture. 10 minuteslater, another 0.169 g of 1,4-bis(4′-fluorobenzoyl)benzene were added tothe reactor and the reaction mixture was kept at temperature for 15minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 56 g of an off-white/yellow powder. Thefinal polymer had a T/I ratio of 60/40. The PEKK polymer was analyzed asdescribed above. The synthesis parameters and results of the analysisare displayed in Tables 1 to 3.

Comparative Example 4: Synthesis and Analysis of PEKK with 60/40 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route.

The procedure of comparative example 3 was repeated except for thefollowing. The monomer weights used were as follows:1,3-bis(4′-hydroxybenzoyl)benzene, 26.739 g;1,4-bis(4′-hydroxybenzoyl)benzene, 6.685 g; and1,4-bis(4′-fluorobenzoyl)benzene, 33.842 g. Additionally, theend-capping procedure was different. In particular, at the end of theaddition, the reaction mixture was heated to 320° C. at 1° C./minute.After 0 minutes at 320° C., 2.115 g of 1,4-bis(4′-fluorobenzoyl)benzenewere added to the reaction mixture while keeping a nitrogen purge on thereactor. After 5 minutes, 0.445 g of lithium chloride were added to thereaction mixture. 10 minutes later, another 0.169 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reactor and thereaction mixture was kept at temperature for 15 minutes. The powderobtained from the synthesis was off-white and had a weight of 56 g. Thefinal polymer had a T/I ratio of 60/40.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

Comparative Example 5: Synthesis and Analysis of PEKK with 60/40 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 127.83 g of diphenyl sulfone, 31.832 g of1,3-bis(4′-hydroxybenzoyl)benzene, 7.958 g of1,4-bis(4′-hydroxybenzoyl)benzene, 13.977 g of Na₂CO₃ and 0.078 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 200° C. At 200° C., 40.771 gof 1,4-bis(4′-fluorobenzoyl)benzene was added via a powder dispenser tothe reaction mixture over 30 minutes. At the end of the addition, thereaction mixture was heated to 320° C. at 1° C./minute. After 82 minutesat 320° C., 0.806 g of 1,4-bis(4′-fluorobenzoyl)benzene were added tothe reaction mixture while keeping a nitrogen purge on the reactor.After 5 minutes, 0.371 g of lithium chloride were added to the reactionmixture. 10 minutes later, another 0.403 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reactor and thereaction mixture was kept at temperature for 15 minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 68 g of an off-white/yellow powder. Thefinal polymer had a T/I ratio of 60/40.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

Example 6: Synthesis and Analysis of PEKK with 60/40 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 127.83 g of diphenyl sulfone, 31.832 g of1,3-bis(4′-hydroxybenzoyl)benzene, 7.958 g of1,4-bis(4′-hydroxybenzoyl)benzene, 13.673 g of Na₂CO₃ and 0.078 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 200° C. At 200° C., 40.771 gof 1,4-bis(4′-fluorobenzoyl)benzene was added via a powder dispenser tothe reaction mixture over 30 minutes. At the end of the addition, thereaction mixture was heated to 320° C. at 1° C./minute. After 7 minutesat 320° C., 1.612 g of 1,4-bis(4′-fluorobenzoyl)benzene were added tothe reaction mixture while keeping a nitrogen purge on the reactor.After 5 minutes, 0.530 g of lithium chloride were added to the reactionmixture. 10 minutes later, another 0.403 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reactor and thereaction mixture was kept at temperature for 15 minutes.

The reactor content was then poured from the reactor into a SS pan andcooled. The solid was broken up and ground in an attrition mill througha 2 mm screen. Diphenyl sulfone and salts were extracted from themixture with acetone and water at pH between 1 and 12. The powder wasthen removed from the reactor and dried at 120° C. under vacuum for 12hours yielding 72 g of an off-white/yellow powder. The final polymer hada T/I ratio of 60/40.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

Example 7: Synthesis and Analysis of PEKK with 60/40 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of Example 6 was repeated, except adding 40.892 g of1,4-bis(4′-fluorobenzoyl)benzene at 200° C. The PEKK polymer wasanalyzed as described above. The synthesis parameters and results of theanalysis are displayed in Tables 1 to 3.

Example 8: Synthesis and Analysis of PEKK with 60/40 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of Comparative Example 3 was repeated, except for thefollowing. The monomer weights used were: 26.739 g of1,3-bis(4′-hydroxybenzoyl)benzene; 6.685 g of1,4-bis(4′-hydroxybenzoyl)benzene; and 34.078 g of1,4-bis(4′-fluorobenzoyl)benzene. Additionally the end-capping procedurewas different. After 12 minutes at 320° C., 0.423 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reaction mixturewhile keeping a nitrogen purge on the reactor. After 5 minutes, 0.445 gof lithium chloride were added to the reaction mixture. 10 minuteslater, another 0.169 g of 1,4-bis(4′-fluorobenzoyl)benzene were added tothe reactor and the reaction mixture was kept at temperature for 15minutes. The powder obtained from the synthesis was off-white and had aweight of 57 g. The final polymer had a T/I ratio of 60/40.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Comparative Example 9: Analysis of PEKK Synthesized by ElectrophilicSynthesis Route

The following example demonstrates the analysis of PEKK synthesizedusing an electrophilic synthesis route. Cypek® FC was analyzed asdescribed above, and the results are displayed in the tables below.

Comparative Examples 10 and 11: Synthesis and Analysis of PEKK with70/30 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route, according to the CN'631application.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 249.93 g of diphenyl sulfone, 39.790 g of1,4-bis(4′-hydroxybenzoyl)benzene, 16.115 g of1,4-bis(4′-fluorobenzoyl)benzene, 24.172 g of 1,3bis(4′-fluorobenzoyl)benzene and 13.646 g of Na₂CO₃. The flask contentwas evacuated under vacuum and then filled with high purity nitrogen(containing less than 10 ppm 02). The reaction mixture was then placedunder a constant nitrogen purge (60 mL/min).

The reaction mixture was heated to 120° C., then from 120° C. to 160° C.at 2° C./min. The mixture was then held at 160° C. for 1 h, heated up to210° C. at 5° C./min and held at 210° C. for 1 h. The mixture was thenheated up to 250° C. at 5° C./min and held at 250° C. for 1 h. Themixture was then heated up to 290° C. at 10° C./min and held at 290° C.for 2 h. The mixture was heated up to 310° C. at 10° C./min and held at310° C. for 3 h. The reactor content was then poured from the reactorinto a stainless steel pan and cooled. The solid was broken up andground in an attrition mill through a 2 mm screen. Diphenyl sulfone andsalts were extracted from the mixture with acetone and water at pHbetween 1 and 12. The powder was then removed from the reactor and driedat 120° C. under vacuum for 12 hours yielding 68 g of anoff-white/yellow powder. The final polymer had a T/I ratio of 70/30.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Comparative Examples 12: Synthesis and Analysis of PEKK with 72/28 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route, according to the CN'631application.

The procedure of Comparative Examples 10 and 11 was repeated except forthe monomer weights, which were as follows: 39.790 g of1,4-bis(4′-hydroxybenzoyl)benzene; 17.726 g of1,4-bis(4′-fluorobenzoyl)benzene; and 22.561 g of1,3-bis(4′-fluorobenzoyl)benzene. The PEKK polymer had a T/I ratio of72/28.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Comparative Example 13: Synthesis and Analysis of PEKK with 70/30 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced an initial charge of 127.83 g of diphenyl sulfone, 23.874 gof 1,3-bis(4′-hydroxybenzoyl)benzene, 15.916 g of1,4-bis(4′-hydroxybenzoyl)benzene, 40.287 g of1,4-bis(4′-fluorobenzoyl)benzene, 12.719 g of Na₂CO₃ and 1.632 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 200° C. and then from 200° C.to 320° C. at 1° C./minute. After 8 minutes at 320° C., the reactorcontent was poured from the reactor into a stainless steel pan andcooled. The solid was broken up and ground in an attrition mill througha 2 mm screen. Diphenyl sulfone and salts were extracted from themixture with acetone and water at pH between 1 and 12. The powder wasthen removed from the reactor and dried at 120° C. under vacuum for 12hours yielding 67 g of an off-white/yellow powder. The final polymer hada T/I ratio of 70/30.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Comparative Example 14: Synthesis and Analysis of PEKK with 71/29 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced an initial charge of 122.31 g of diphenyl sulfone, 29.540 gof 1,3-bis(4′-hydroxybenzoyl)benzene, 10.151 g of Na₂CO₃ and 0.100 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 200° C. At 200° C., a secondcharge of 30.268 g of 1,4-bis(4′-fluorobenzoyl)benzene, were added via apowder dispenser to the reaction mixture over 30 minutes. At the end ofthe addition, the reaction mixture was heated to 240° C. at 1°C./minute.

At 240° C., a third charge of a mixture of 21.919 g of1,4-bis(4′-fluorobenzoyl)benzene, 21.391 g of1,4-bis(4′-hydroxybenzoyl)benzene and 7.350 g of Na₂CO₃ was added slowlyto the reaction mixture over 30 minutes.

At the end of the addition, the reaction mixture was heated to 320° C.at 1° C./minute. To end-cap the PEKK polymer, after 3 minutes at 320°C., 4.126 g of 1,4-bis(4′-fluorobenzoyl)benzene were added to thereaction mixture while keeping a nitrogen purge on the reactor. After 5minutes, 0.679 g of lithium chloride were added to the reaction mixture.10 minutes later, another 0.516 g of 1,4-bis(4′-fluorobenzoyl)benzenewere added to the reactor and the reaction mixture was kept attemperature for 15 minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 90 g of a yellow powder. The final polymerhad a T/I ratio of 71/29.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Comparative Example 15: Synthesis and Analysis of PEKK with 71/28 T/IRatio

This example demonstrates the synthesis of a PEKK polymer via atraditional nucleophilic synthetic route.

The procedure of Comparative Example 13 was repeated, except for thefollowing reagent weights: 127.83 g of diphenyl sulfone; 39.790 g of1,4-bis(4′-hydroxybenzoyl)benzene; 13.309 g of Na₂CO₃; 0.864 g of K₂CO₃;17.726 g of 1,4-bis(4′-fluorobenzoyl)benzene; and 22.561 g of1,3-bis(4′-fluorobenzoyl)benzene. After 7 minutes at 320° C., dischargeof reaction mixture. The final polymer weight (off-white powder) was 49g and the final polymer had a T/I ratio of 71/28.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 16: Synthesis and Analysis of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced an initial charge of 102.27 g of diphenyl sulfone, 18.463 gof 1,3-bis(4′-hydroxybenzoyl)benzene, 6.344 g of Na₂CO₃ and 0.062 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 200° C. At 200° C., a secondcharge of 18.918 g of 1,4-bis(4′-fluorobenzoyl)benzene, were added via apowder dispenser to the reaction mixture over 30 minutes. At the end ofthe addition, the reaction mixture was heated to 240° C. at 1°C./minute.

At 240° C., a third charge of a mixture of 13.699 g of1,4-bis(4′-fluorobenzoyl)benzene, 13.370 g of1,4-bis(4′-hydroxybenzoyl)benzene and 4.595 g of Na₂CO₃ was added slowlyto the reaction mixture over 30 minutes.

At the end of the addition, the reaction mixture was heated to 320° C.at 1° C./minute. The end capping procedure was as follow: After 150minutes at 320° C., 1.290 g of 1,4-bis(4′-fluorobenzoyl)benzene wereadded to the reaction mixture while keeping a nitrogen purge on thereactor. After 5 minutes, 0.424 g of lithium chloride were added to thereaction mixture. 10 minutes later, another 0.323 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reactor and thereaction mixture was kept at temperature for 15 minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 52 g of an off-white/yellow powder. Thefinal polymer had a T/I ratio of 71/29. The PEKK polymer was analyzed asdescribed above. The synthesis parameters and results of the analysisare displayed in the tables below.

Example 17: Synthesis and Analysis of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 16 was followed except for the following:

-   -   Initial charge: 132.71 g of Diphenyl Sulfone; 29.540 g        1,3-bis(4′-hydroxybenzoyl)benzene; 10.151 g of Na₂CO₃; and 0.100        g of K₂CO₃;    -   Second Charge: 30.268 g of 1,4-bis(4′-fluorobenzoyl)benzene;    -   Third Charge: added at 240° C. were 21.391 g of        1,4-bis(4′-hydroxybenzoyl)benzene; 21.918 g of        1,4-bis(4′-fluorobenzoyl)benzene; and 7.350 g Na₂CO₃.

The final polymer had a T/I ratio of 71/29 and a weight of 90 g.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 18: Synthesis and Analysis of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 14 was followed except with the following:

-   -   Initial Charge: 126.13 g of diphenyl sulfone; 25.848 g        1,3-bis(4′-hydroxybenzoyl)benzene; 8.882 g of Na₂CO₃; and 0.087        g of K₂CO₃    -   Second Charge: 26.485 g of 1,4-bis(4′-fluorobenzoyl)benzene;    -   Third Charge: 18.717 g of 1,4-bis(4′-hydroxybenzoyl)benzene;        19.179 g of 1,4-bis(4′-fluorobenzoyl)benzene; 6.432 g Na₂CO₃;    -   End-Capping: After 12 minutes at 320° C., 3.610 g of        1,4-bis(4′-fluorobenzoyl)benzene; after another 5 minutes, 0.594        g of lithium chloride; after another 10 minutes, 0.451 g of        1,4-bis(4′-fluorobenzoyl)benzene.

The final polymer had a T/I ratio of 71/29 and a weight of 80 g.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

Example 19: Synthesis and Analysis of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 14 was followed except with the following:

-   -   Initial Charge: 129.91 g of diphenyl sulfone; 14.770 g        1,3-bis(4′-hydroxybenzoyl)benzene; 5.075 g of Na₂CO₃; and 0.050        g of K₂CO₃    -   Second Charge: 15.134 g of 1,4-bis(4′-fluorobenzoyl)benzene;    -   Third Charge: 10.696 g of 1,4-bis(4′-hydroxybenzoyl)benzene;        10.959 g of 1,4-bis(4′-fluorobenzoyl)benzene; 3.675 g Na₂CO₃;    -   End-Capping: After 9 minutes at 320° C., 2.063 g of        1,4-bis(4′-fluorobenzoyl)benzene; after another 5 minutes, 0.339        g of lithium chloride; after another 10 minutes, 0.258 g of        1,4-bis(4′-fluorobenzoyl)benzene.

The final polymer had a T/I ratio of 71/29 and a weight of 80 g.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 20: Synthesis and Analysis of PEKK with 72/28 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 102.27 g of diphenyl sulfone, 31.832 g of1,4-bis(4′-hydroxybenzoyl)benzene, 14.280 g of1,4-bis(4′-fluorobenzoyl)benzene and 18.175 g of 1,3bis(4′-fluorobenzoyl)benzene. The flask content was evacuated undervacuum and then filled with high purity nitrogen (containing less than10 ppm 02). The reaction mixture was then placed under a constantnitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 180° C. At 180° C., 11.023 gof Na₂CO₃ were added via a powder dispenser to the reaction mixture over30 minutes. At the end of the addition, the reaction mixture was heatedto 310° C. at 1° C./minute. After 150 minutes at 310° C., 0.645 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reaction mixturewhile keeping a nitrogen purge on the reactor. After 5 minutes, 0.424 gof lithium chloride were added to the reaction mixture. 10 minuteslater, another 0.323 g of 1,4-bis(4′-fluorobenzoyl)benzene were added tothe reactor and the reaction mixture was kept at temperature for 15minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 52 g of an off-white/yellow powder. Thefinal polymer had a T/I ratio of 72/28.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

Example 21: Synthesis and Analysis of PEKK with 72/28 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced an initial charge 102.27 g of diphenyl sulfone, 31.832 g of1,4-bis(4′-hydroxybenzoyl)benzene, 14.280 g of1,4-bis(4′-fluorobenzoyl)benzene and 18.175 g of1,3-bis(4′-fluorobenzoyl)benzene. The flask content was evacuated undervacuum and then filled with high purity nitrogen (containing less than10 ppm 02). The reaction mixture was then placed under a constantnitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 180° C. At 180° C., a secondcharge of 11.023 g of Na₂CO₃ were added via a powder dispenser to thereaction mixture over 30 minutes. At the end of the addition, thereaction mixture was heated to 310° C. at 1° C./minute. To end-cap thePEKK polymer, after 150 minutes at 310° C., 0.645 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reaction mixturewhile keeping a nitrogen purge on the reactor. After 5 minutes, 0.424 gof lithium chloride were added to the reaction mixture. 10 minuteslater, another 0.323 g of 1,4-bis(4′-fluorobenzoyl)benzene were added tothe reactor and the reaction mixture was kept at temperature for 15minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 52 g of an off-white/yellow powder. Thefinal polymer had a T/I ratio of 72/28.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 22: Synthesis and Analysis of PEKK with 72/28 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 21 was followed except with the following:

-   -   Initial Charge: 102.27 g diphenyl sulfone; 14.006 g of        1,4-bis(4′-hydroxybenzoyl)benzene; 17.826 g of        1,3-bis(4′-hydroxybenzoyl)benzene; and 11.024 g of Na₂CO₃    -   Second Charge: 32.456 g of 1,4-bis(4′-fluorobenzoyl)benzene;    -   End-Capping: After 92 minutes at 310° C., 0.645 g of        1,4-bis(4′-fluorobenzoyl)benzene; after another 5 minutes, 0.426        g of lithium chloride; after another 10 minutes, 0.322 g of        1,4-bis(4′-fluorobenzoyl)benzene.

The final polymer had a T/I ratio of 72/28 and a weight of 54 g.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 23: Synthesis and Analysis of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 14 was followed except with the following:

-   -   Initial Charge: 102.72 g of diphenyl sulfone; 18.463 g        1,3-bis(4′-hydroxybenzoyl)benzene; 6.332 g of Na₂CO₃; and 0.040        g of K₂CO₃    -   Second Charge: 18.918 g of 1,4-bis(4′-fluorobenzoyl)benzene;    -   Third Charge: 13.369 g of 1,4-bis(4′-hydroxybenzoyl)benzene;        13.699 g of 1,4-bis(4′-fluorobenzoyl)benzene; 4.585 g Na₂CO₃;        and 0.029 g of K₂CO₃    -   End-Capping: After 5 minutes at 320° C., 2.063 g of        1,4-bis(4′-fluorobenzoyl)benzene; after another 5 minutes, 0.339        g of lithium chloride; after another 10 minutes, 0.258 g of 1,4        bis(4′-fluorobenzoyl)benzene.

The final polymer had a T/I ratio of 71/29 and a weight of 54 g.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 24: Synthesis and Analysis of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced an initial charge 102.27 g of diphenyl sulfone, 18.463 g of1,3-bis(4′-hydroxybenzoyl)benzene, 6.363 g of Na₂CO₃ and 0.024 g ofK₂CO₃. The flask content was evacuated under vacuum and then filled withhigh purity nitrogen (containing less than 10 ppm 02). The reactionmixture was then placed under a constant nitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 180° C. At 180° C., a secondcharge of 18.918 g of 1,4-bis(4′-fluorobenzoyl)benzene, were added via apowder dispenser to the reaction mixture over 30 minutes. At the end ofthe addition, the reaction mixture was heated to 220° C. at 1°C./minute. At 220° C., a third charge containing a mixture of 13.699 gof 1,4-bis(4′-fluorobenzoyl)benzene, 13.369 g of1,4-bis(4′-hydroxybenzoyl)benzene, 4.607 g of Na₂CO₃ and 0.017 g ofK₂CO₃ was added slowly to the reaction mixture over 30 minutes.

At the end of the addition, the reaction mixture was heated to 320° C.at 1° C./minute. To end-cap the PEKK polymers, after 10 minutes at 320°C., 2.578 g of 1,4-bis(4′-fluorobenzoyl)benzene were added to thereaction mixture while keeping a nitrogen purge on the reactor. After 5minutes, 0.213 g of lithium chloride were added to the reaction mixture.10 minutes later, another 0.322 g of 1,4-bis(4′-fluorobenzoyl)benzenewere added to the reactor and the reaction mixture was kept attemperature for 15 minutes.

The reactor content was then poured from the reactor into a stainlesssteel pan and cooled. The solid was broken up and ground in an attritionmill through a 2 mm screen. Diphenyl sulfone and salts were extractedfrom the mixture with acetone and water at pH between 1 and 12. Thepowder was then removed from the reactor and dried at 120° C. undervacuum for 12 hours yielding 47 g of a off-white/yellow powder. Thefinal polymer had a T/I ratio of 71/29.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 25: Preparation of PEKK with 71/29 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 24 was followed, except for the following:

-   -   Initial Charge: 102.27 g of Diphenyl sulfone; 13.369 g of        1,4-bis(4′-hydroxybenzoyl)benzene; 18.463 g of        1,3-bis(4′-hydroxybenzoyl)benzene; 10.938 g of Na₂CO₃; and 0.276        g of K₂CO₃    -   Second Charge: 32.617 g of 1,4-bis(4′-fluorobenzoyl)benzene    -   End-Caping: after 5 minutes at 320° C., addition of 1.289 g        4-bis(4′-fluorobenzoyl)benzene; after another 5 min., addition        of 0.426 g lithium chloride; and after another 10 min., addition        of 0.322 g of 1,4-bis(4′-fluorobenzoyl)benzene.

The final polymer had a T/I ratio of 71/29 and a weight of 54 g.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Example 26: Synthesis and Analysis of PEKK with 72/28 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

The procedure of example 13 was followed except with the following:

-   -   Initial Charge: 251.35 g of diphenyl sulfone; 39.790 g of        1,4-bis(4′-hydroxybenzoyl)benzene; 17.726 g of        1,4-bis(4′-fluorobenzoyl)benzene; 22.561 g of        1,3-bis(4′-fluorobenzoyl)benzene; 13.673 g of Na₂CO₃; and 0.078        g of K₂CO₃    -   After 32 minutes at 320° C., the reaction mixture was discharged

The final polymer was an off-white powder having a weight of 74 g and aT/I ratio of 72/28.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in the tablesbelow.

Results

Tables 1 and 2 display a summary of the synthesis conditions for each ofthe examples. In the tables, the following abbreviations are used:14BHBB refers to 1,4-bis(4′-hydroxybenzoyl)benzene; 13BHBB refers to1,3-bis(4′-hydroxybenzoyl)benzene; 14DFDK refers to1,4-bis(4′-fluorobenzoyl) benzene; and 13DFDK refers to1,3-bis(4′-fluorobenzoyl)benzene.

Example 27: Synthesis and Analysis of PEKK with 60/40 T/I Ratio

This example demonstrates the synthesis of a PEKK polymer via anucleophilic synthetic route.

In a 500 mL 4-neck reaction flask fitted with a stirrer, a N₂ inlettube, a Claisen adapter with a thermocouple plunging in the reactionmedium, and a Dean-Stark trap with a condenser and a dry ice trap wereintroduced 127.50 g of diphenyl sulfone, 33.390 g of1,3-bis(4′-hydroxybenzoyl)benzene, 6.360 g of1,4-bis(4′-hydroxybenzoyl)benzene and 40.810 g of1,4-bis(4′-fluorobenzoyl)benzene. The flask content was evacuated undervacuum and then filled with high purity nitrogen (containing less than10 ppm 02). The reaction mixture was then placed under a constantnitrogen purge (60 mL/min).

The reaction mixture was heated slowly to 280° C. At 280° C., 13.743 gof Na₂CO₃ and 0.086 g of K₂CO₃. was added via a powder dispenser to thereaction mixture over 60 minutes. At the end of the addition, thereaction mixture was heated to 320° C. at 1° C./minute. After 100minutes at 320° C., 1.207 g of 1,4-bis(4′-fluorobenzoyl)benzene wereadded to the reaction mixture while keeping a nitrogen purge on thereactor. After 5 minutes, 0.530 g of lithium chloride were added to thereaction mixture. 10 minutes later, another 0.503 g of1,4-bis(4′-fluorobenzoyl)benzene were added to the reactor and thereaction mixture was kept at temperature for 15 minutes.

The reactor content was then poured from the reactor into a SS pan andcooled. The solid was broken up and ground in an attrition mill througha 2 mm screen. Diphenyl sulfone and salts were extracted from themixture with acetone and water at pH between 1 and 12. The powder wasthen removed from the reactor and dried at 120° C. under vacuum for 12hours yielding 72 g of an off-white/yellow powder. The final polymer hada T/I ratio of 60/40.

The PEKK polymer was analyzed as described above. The synthesisparameters and results of the analysis are displayed in Tables 1 to 3.

TABLE 1 mol % mol Na₂CO₃; 14BHBB mol K₂CO₃ (relative (relative to mol tomol Add#1 13BHBB + [monomers] 13BHBB + % XS (reagent, T Example 14BHBB)(wt %) 14BHBB) DFDK in ° C.) Σ CE1 CE2a 100 25 1.030/0.00 0.0  7* CE2b100 25 1.030/0.00 0.0  7* CE3 20 39 1.037/0.0050 −2.0 DFDK, 200  4.2*CE4 20 39 1.037/0.0050 0.0 DFDK, 200  2.2* CE5 20 39 1.055/0.0045 1.2DFDK, 200  3.1* 6 20 39 1.032/0.0045 1.2 DFDK, 200  0.8 7 20 391.032/0.0045 1.5 DFDK, 200  0.5 8 20 39 1.037/0.0050 2.5 DFDK, 200 −0.327 16 42 1.037/0.0050 1.4 Carbonates,  1.6 280

TABLE 2 mol % mol Na₂CO₃; 14BHBB mol K₂CO₃ (relative (relative to to molmol Add#1 13BHBB + [monomers] 13BHBB + % XS (reagent, Example T/I14BHBB) (wt %) 14BHBB) DFDK T in ° C.) Σ CE9 CE10 70/30 100 251.030/0.0000 0  7.0* CE11 70/30 100 25 1.030/0.0000 0  7.0* CE12 72/28100 25 1.030/0.0000 0 0  7.0* CE13 70/30 42 39  .960/0.09450* 0 0 42.2*CE14 71/29 42  48* 1.032/0.00450 1.2 DFDK,  3.1 200 CE15 72/28 100 391.005/0.050* 0.0 0 20.0* 16 71/29 42 39 1.032/0.0045/1 1.2 DFDK,  0.8200 17 71/29 42 44 1.032/0.0045/1 1.2 DFDK,  2.1 200 18 71/29 42 421.032/0.0045/1 1.2 DFDK,  1.6 200 19 71/29 42 29 1.032/0.0045/1 1.2DFDK,  2.3 200 20 72/28 100 39 1.040/0.000/1 0.7 Na2CO3,  4.8 180 2172/28 72 39 1.040/0.000/1 0.7 DFDK,  4.8 180 22 72/28 44 391.040/0.000/1 0.7 DFDK,  4.8 180 23 71/29 42 39 1.030/0.0040/1 1.2 DFDK, 0.9 200 24 71/29 42 39 1.035/0.0030/1 1.2 DFDK,  2.0 180 25 71/29 42 391.032/0.020/1 1.2 DFDK,  3.5 180 26 72/28 100 25 1.032/0.0045/1 0.0 0 4.5

Referring to Tables 1 and 2, the column “Add #1” refers to the additionof a reagent in the reaction mixture after the initial charge and beforethe end-capping procedure (during a first heating). The PEKK polymersmade by a nucleophilic route in Table 1 have a T/I ratio of 60/40, whilethose in Table 2 vary from 70/30 to 72/28. Additionally, in Tables 1 and2, as well as Tables 3-6 below, values denoted with an “*” indicatevalues that do not satisfy the prescribed quantities according toFormulae (EQ1)-(EQ4).

The physical and mechanical properties of the synthesized PEKK polymerscorresponding to the samples of Tables 1 and 2 are displayed in Tables3-6. In Tables 3 and 4, values denoted with a “†” indicate a ΔMV that isgreater than 0.

TABLE 3 Example CE1 CE2a CE2b CE3 CE4 CE5 6 7 8 27 Σ   7*   7*   4.2*  2.2*   3.1* 0.8 0.5 −0.3 1.6 η_(inh) 1.07   1.70   1.31   1.15   1.31  1.35 1.28 1.58 1.26 0.94 (dL/g) MV 753  9225  3563 19328 3260  39412622 5832 2198 575 (410° C.) MV^(exp)  7968  2884  1735 2884  3243 26345989 2478 790 (Pa · s) 1006 IV{circumflex over ( )}3.9 ΔMV-  1257†  679†17593†  376†  698† −12 −157 −280 −215 MV^(exp) (Pa · s) Tensile 1180012200 12200 11900 12800 11670 13100 strength at yield (psi) Elong at 5.0  5.5   5.5   5.2 5.2 5.2 4.7 yield (%) Elong at 35   36   36   40 43 5112 break (%) Tensile 421  421  421  419 445 420 478 modulus (kpsi) [CI]5750  <70  <70 <70 28 21 (ppm) Td(1%) 365  517  528 528 516 543 530 (°C.)

TABLE 4 Example CE9 CE10 CE11 CE12 CE13 CE14 CE15 Σ   7.0*   7.0*   7.0*   42.2*   3.1  20.0* Add #1    0   0 DFDK,   0 (reagent, T  200in ° C.) η_(inh) (dL/g)   1.00   1.54   1.52    1.95   1.06   1.11  1.33 MV (380° C.)  520  9123  8151 >30000  1875  4203 6655 Exp MV 1490  8297  7876  21219  1877  2255 4636 (Pa · s) ΔMV (Pa · s)  −970 826†  275†  >8781†   −2†  1948† 2019† Td(1%)  3733  514   511 (° C.)[CI] (ppm)  1825 Tensile 16000ª 11500 14996  12900 16200 17161 strengthat yield (psi) Elong at   0   5.5   5.0    5.3   4.6   4.2 yield (%)Elong at   3.0   45   24   29   16   6.4 break (%) Tensile  666  408 525   442  561  602 modulus (kpsi)

TABLE 5 Example 16 17 18 19 20 Σ 0.8 2.1 1.6 2.3 4.8 Add#1 DFDK, 200DFDK, 200 DFDK, 200 DFDK, 200 Na₂CO₃, 180 (reagent, T in ° C.) η_(inh)(dL/g) 0.82 1.02 0.91 1.28 0.83 MV (380° C.) 503 1527 919 3587 618 ExpMV 676 1611 1023 3976 710 (Pa · s) ΔMV (Pa · s) −173 −84 −104 −389 −92Td(1%) (° C.) 510 [Cl] (ppm) 53 Tensile 17300 17300 N/A strength atyield (psi) Elong at yield 4.6 4.4 N/A (%) Elong at 10 6.9 N/A break (%)Tensile 594 621 N/A modulus (kpsi)

TABLE 6 Example 21 22 23 24 25 26 Σ 4.8 4.8 0.9 2.0 3.5 4.5 Add#1 DFDK,DFDK, DFDK, DFDK, DFDK, 0 (reagent, T 180 180 200 180 180 in ° C.)η_(inh) (dL/g) 1.11 1.30 0.82 0.89 0.84 1.51 MV (380° C.) 1415 2224 494710 583 6142 Exp MV 2255 4229 676 937 744 7683 (Pa · s) ΔMV (Pa · s)−840 −2005 −182 −227 −161 −1541 Td(1%) 511 (° C.) [CI] (ppm) Tensile16500 16700 strength at yield (psi) Elong at 4.6 6.1 yield (%) Elong at10 11 break (%) Tensile 704 690 modulus (kpsi)

Referring to Tables 1 to 6, the PEKK polymers synthesized using thereaction components within the prescribed quantities (i.e., according toFormula (EQ1) to (EQ4)) had a unexpectedly lower melt viscosity (“MV”)for a given η_(inh), relative to PEKK polymers synthesized usingreaction components outside the prescribed quantities. The ΔMV wasdetermined according to Formula (E1) and (E2). The expected MV, MV (e),for (comparative) examples 1 to 8 and 27 (T/I ratio within the range55/45 to 65/35) were determined by measuring and plotting MV vs. η_(inh)for the PEKK polymers of comparative examples 1 to 5 and fitting to thecurve MV=m_(mv)η_(inh) ^(n). Similarly, the expected MV, MV (e), for(comparative) examples 9 to 26 (T/I ratio within the range of greaterthan 65/35 to 75/25) were determined by measuring and plotting MV vs.η_(inh) for the PEKK polymers of comparative examples 9 to 15 andfitting to the curve MV=m_(mv)η_(inh) ^(n). For the PEKK polymers of(comparative) examples 1 to 8 and 27, m_(mv)=1006 (Pa·s)(g/dL)^(3.90)and n=3.90; and for the PEKK polymers of comparative examples 9 to 26,m_(mv)=1490 (Pa·s)(g/dL)^(3.98) and n=3.98.

Referring to Tables 1 and 3 (PEKK polymers having a T/I ratio from 55/45to 65/35), the PEKK polymers synthesized using reaction componentswithin the prescribed quantities had an unexpectedly lower MV for agiven η_(inh), relative to the PEKK polymers synthesized using reactioncomponents outside the prescribed quantities. For example, the PEKKpolymers of examples 6 to 8 and 27 had a ΔMV that was −2 Pa·s or less.In contrast, the ΔMV for each of comparative examples 2 to 5 had a ΔMVthat was greater than −2 Pa·s. It is noted that for examples 6 to 8 and27, Σ<2.0 (reaction components within the prescribed quantities for T/Iratio from 55/45 to 65/35), while for Comparative Examples 2 to 5, Σ>2.0(reaction components outside the prescribed quantities for T/I ratiofrom 55/45 to 65/35). Referring to Tables 2 and 4-6, similar resultswere seen for PEKK polymers having a T/I ratio greater than 65/35 to75/25. In particular, examples 16 to 26 each had a ΔMV that was lessthan −2 Pa·s, while Comparative Examples 10 to 15 each had a ΔMV thatwas greater than −2 Pa·s. Again, it is noted that for examples 16 to 26,Σ<6.0 (reaction components within the prescribed quantities for T/Iratio more than 65/35 to 75/25) and, for Comparative Examples 10 to 13and 15, Σ>6.00 (outside the prescribed quantities for T/I ratio morethan 65/35 to 75/25). Comparative Example 14, on the other hand, had aΣ<6.0, but a ΔMV of 1948 Pa·s (significantly greater than −2 Pa·s).However, the % Monomers in the synthesis method of Comparative Example14 was 48 wt. %, outside the prescribed range of from 25 wt. % to 44 wt.%, indicated in Formula (EQ4).

Furthermore, referring to Tables 1 and 3, the PEKK polymers of examples6 to 8 had significantly increased elongation at break, relative tocomparative examples 2 to 5, while exhibiting a lower MV. In particular,the elongation at break for examples 6 and 7 was 43% and 51%,respectively, while that of the comparative examples 2 to 5 ranged from35% to 40%.

Additionally, for the PEKK polymers tested, the PEKK polymerssynthesized via a nucleophilic route had improved improved Td(1%),relative to PEKK polymers synthesized via a electrophilic route.Referring to Tables 1 and 3, the Td(1%) for the PEKK polymer of examples6 to 8 and 27 was higher than 500° C., while that of the PEKK polymersof comparative example 1, was 365° C. Similarly, referring to Tables 2and 4-6, Td(1%) for the PEKK polymer or examples 16 and 22 was 510° C.and 511° C., respectively ° C., while that of the PEKK polymers ofcomparative example 9, was 373° C. Additionally, relative to PEKKpolymers synthesized using an electrophilic route, the PEKK polymersdescribed herein have significantly reduced residual chlorine content.For example, examples 7 and 8 (nucleophilic synthesis route) had atleast a 99.5% reduction in residual chlorine, relative to ComparativeExample 1 (electrophilic synthesis route). Similarly, example 16(nucleophilic synthesis route) had a 97.1% reduction in residualchlorine, relative to Comparative Example 9 (electrophilic synthesisroute).

Should the disclosure of any patents, patent applications, andpublications which are incorporated herein by reference conflict withthe description of the present application to the extent that it mayrender a term unclear, the present description shall take precedence.

1. A method of forming a poly(ether ketone ketone), (PEKK) polymer,comprising at least one recurring unit (R^(M) _(PEKK)) and at least onerecurring unit (R^(P) _(PEKK)), the method comprising: reacting, in areaction mixture, a blend of one or more bis(hydroxybenzoyl) benzenemonomer and one or more bis(halobenzoyl) benzene monomers in thepresence of Na₂CO₃, K₂CO₃ and a solvent, whereinΣ=(% Na₂CO₃−105)+6*|% K₂CO₃−1|+0.25*β7−% Monomers|−% XS_(DFDK),  (EQ1)0%≤% K₂CO₃<5%, and  (EQ2)0%≤% XS_(DFDK),  (EQ3)25%≤% Monomers≤44%, and  (EQ4) wherein: Σ<6 % Na₂CO₃ is theconcentration, in mol %, of Na₂CO₃, relative to the number of moles ofthe one or more bis(hydroxybenzoyl) benzene monomers; % K₂CO₃ is theconcentration, in mol %, of K₂CO₃, relative to the number of moles ofthe one or more bis(hydroxybenzoyl) benzene monomers and where % K₂CO₃ranges from 0 mol % to less than 5 mol %; % Monomers is the totalconcentration, in wt. %, of the one or more bis(hydroxybenzoyl) benzenemonomers and the one or more bis(halobenzoyl) benzene monomers, relativeto the total weight of the one or more bis(hydroxybenzoyl) benzenemonomers, the one or more bis(halobenzoyl) benzene monomers and solventand where % Monomers is from 25 wt. % to 44 wt. % % XS_(DFDK) is theconcentration, in mol %, of the one or more bis(halobenzoyl) benzenemonomers in excess of an equimolar concentration of the one or morebis(hydroxybenzoyl) benzene monomers, and wherein, eachbis(hydroxybenzoyl) benzene monomer and each bis(halobenzoyl) benzenemonomer is distinctly and independently represented by a formulaselected from the following group of formulae:X⁵-M_(m)-X⁵, and  (13)X⁶-M_(p)-X⁶,  (14) wherein X⁵ and X⁶ are an —OH for bis(hydroxybenzoyl)benzene monomers and X⁵ and X⁶ are a halogen for bis(halobenzoyl)benzene monomers, and M_(m) and M_(p) are represented by the followingformulae, respectively,

wherein R¹ and R², at each instance, is independently selected from thegroup consisting of an alkyl, an alkenyl, an alkynyl, an aryl, an ether,a thioether, a carboxylic acid, an ester, an amide, an imide, an alkalior alkaline earth metal sulfonate, an alkyl sulfonate, an alkali oralkaline earth metal phosphonate, an alkyl phosphonate, an amine, and aquaternary ammonium; and i and j, at each instance, is an independentlyselected integer ranging from 0 to 4 and wherein the ratio of the totalnumber of moles of 1,4-bis(hydroxybenzoyl) benzene monomers and1,4-bis(halobenzoyl) benzene monomers that are represented by Formula(14) to the total number of moles of 1,3-bis(hydroxybenzoyl) benzenemonomers and 1,3-bis(halobenzoyl) benzene monomers that are representedby Formula (13) (“(R^(P) _(PEKK))/(R^(M) _(PEKK)) ratio”) is from 55/45to 75/25 and wherein each recurring unit (R^(M) _(PEKK)) and eachrecurring unit (R^(P) _(PEKK)) are represented by the followingformulae, respectively,-[-M_(m)-O—]—, and  (1)-[-M_(p)-O—]—  (2).
 2. The method of claim 1, wherein % K₂CO₃>0 mol %.3. The method of claim 1, wherein % Na₂CO₃+% K₂CO₃≤106.0 mol %.
 4. Themethod of claim 1, wherein 0.1 mol %≤% XS_(DFDK)≤4.0 mol %
 5. The methodof claim 1, wherein the reacting further comprises a first heatingincluding heating the reaction mixture to maintain its temperaturewithin a first temperature range of from 180° C. to 270° C.
 6. Themethod of claim 5, wherein the first heating comprises maintaining thetemperature of the reaction mixture with a first temperature range offrom 180° C. to 270° C. for a first time period of from 5 min. to 300min.
 7. The method of claim 5, wherein the reacting further comprises asecond heating, subsequent to the first heating, wherein the secondheating comprises heating the reaction mixture to a temperature from300° C. to 340° C.
 8. The method of claim 7, wherein the second heatingfurther comprises maintain the reaction mixture within a secondtemperature range from 300° C. to 340° C. for a second period of timeranging from less than 1 min. to 240 min., preferably to 180 min, mostpreferably to 120 min.
 9. The method of claim 7, wherein the secondheating further comprises adding an end-capping agent to the reactionmixture, the end-capping agent is selected from the group consisting of:

an excess of the one or more bis(halobenzoyl) benzene monomers, and acombination thereof, wherein G is —C(O)—Ar or S(O2)-Ar, and Ar is anarylene group.
 10. The method of claim 1, wherein (a) the (R^(P)_(PEKK))/(R^(M) _(PEKK)) ratio is greater than 65/35 to 75/25, and (b)ΔMV that is no more than −2 Pa·s, whereinMV=MV^((e))−MV and  (E1)MV^((e)) =m _(mv)η_(inh), and  (E2) wherein: MV is the melt viscositymeasured according to ASTM D3835 at 380° C. and 46 s-1 with a diediameter=1.016 mm, length=20.32 mm, cone angle=120° η_(inh) is theinherent viscosity measured according to ASTM D2857 using a testingtemperature of 30° C. and a testing solution comprising 0.5 wt./vol. %solution of the PEKK polymer in concentrated H₂SO₄, and m_(mv)=1490(Pa·s)(g/dL)^(3.98) and n=3.98.
 11. The method of claim 1, wherein (a)the (R^(P) _(PEKK))/(R^(M) _(PEKK)) ratio is from 55/45 to 65/35, (b)Σ<2, and (c) ΔMV that is no more than −2 Pa·s, whereinMV=MV^((e))−MV and  (E1)MV^((e)) =m _(mv)η_(inh), and  (E2) wherein: MV is the melt viscositymeasured according to ASTM D3835 at 410° C. and 46 s-1 with a diediameter=1.016 mm, length=20.32 mm, cone angle=120°, η_(inh) is theinherent viscosity measured according to ASTM D2857 using a testingtemperature of 30° C. and a testing solution comprising 0.5 wt./vol. %solution of the PEKK polymer in concentrated H₂SO₄, and m_(mv)=1006(Pa·s)(g/dL)^(3.90) and n=3.90.
 12. The method of claim 1, wherein afirst monomer of either the one or more bis(hydroxybenzoyl) benzenemonomers or the one or more bis(halobenozyl) benzene monomers isrepresented by a formulaX¹-M¹*_(m)-X¹,  (16) and wherein a second monomer, third monomer andfourth monomer of either the one or more bis(hydroxybenzoyl) benzenemonomers or the one or more bis(halobenozyl) benzene monomers arerespectively represented by the following formulae:X²-M¹*_(p)-X²,  (17)X³-M²*_(p)-X³, and  (18)X⁴-M³*_(p)-X⁴,  (19) wherein (a) X¹ is an —OH or halogen, (b) X² is ahalogen if X¹ is —OH and X² is an —OH if X¹ is a halogen (c) X³ is —OHor a halogen and (d) X⁴ is a halogen if X³ is an —OH and X⁴ is —OH if X³is a halogen and wherein (a) M¹*_(m), M¹*_(p), M²*_(p), and M³*_(p) arerepresented by the following formulae, respectively:

wherein R¹*, R²*, R³* and R⁴*, at each instance, is independentlyselected from the group consisting of an alkyl, an alkenyl, an alkynyl,an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide,an imide, an alkali or alkaline earth metal sulfonate, an alkylsulfonate, an alkali or alkaline earth metal phosphonate, an alkylphosphonate, an amine, and a quaternary ammonium; and i*, j*, k* and L*,at each instance, is an independently selected integer ranging from 0 to4; and wherein the at least one recurring unit (R^(M) _(PE)) comprises arecurring unit (R^(M1) _(PEKK)) represented by the formula:-[-M¹*_(m)-O—]—  and (5) and the at least one recurring unit (R^(P)_(PEKK)) comprises recurring units (R^(P1) _(PEKK)), (R^(P2) _(PE)), and(R^(P3) _(PEKK)), represented by the following formula, respectively:-[-M¹*_(p)-O—]—,  (6)-[-M²*_(p)-O—]—, and  (7)[-M³*_(p)-O—]—  (8).
 13. The method of claim 12, wherein the ratio ofthe number of moles of recurring units (R^(P1) _(PEKK)), (R^(P2) _(PE)),and (R^(P3) _(PE)) to the number of moles of recurring unit (R^(M1)_(PEKK)) is greater than 65/35 to 75/25 or from 55/45 to 65/35.
 14. Themethod of claim 12, wherein (a) the concentration of recurring unit(R^(M1) _(PEKK)) is at least 80 mol %, relative to the total number ofmoles of recurring units (R^(M) _(PEKK)) and (b) the total concentrationof recurring units (R^(P1) _(PEKK)), (R^(P2) _(PEKK)), and (R^(P3)_(PEKK)) is at least 80 mol %, relative to the total number of moles ofrecurring units (R^(P) _(PEKK)) or wherein (a) the total concentrationof recurring units (R^(M) _(PEKK)) and (R^(P) _(PEKK)) is at least 80mol %, relative to the total number of moles of recurring units in thePEKK polymer and
 15. The method of claim 1, wherein X⁵ and X⁶ are Cl andF for bis(halobenzoyl) benzene monomers.